Match



Patented June 23, 1942 MATCH Carleton Ellis, Montelair, N. J., assignor to Standard Oil Development Company, a corporation Delaware No Drawing.

Application December 9, 1939,

Serial No. 308,391 3 Claims. (Cl. 52-25) This invention relates to matches and specifically to compositions oi matterthat improve the burning properties of matches and flame transmission from the match head to the match body. It also involves employment of compositions of matter which are particularly effective in augmenting the burning and igniting qualities or matches and which contain nitrated hydrocarbons or oxygenated derivatives of nitrated hydrocarbons.

Heads of matches ordinarily contain combustibles, materials for supplying oxygen, binding agents, fillers and sometimes waterproofing compounds. Combustibles may be phosphorus, phosphorus sesqui-sulphide, antimony trisulphide or other compounds that are readily ignitible by friction. Peroxides, nitrates, chlorates and perchlorates of metals are used as sources ofoxygen. Water-soluble glues or gums are used as binding agents. Fillers commonly employed are powdered glass, pumice stone, sand, chalk, plaster of Paris, pulverized asbestos, siliceous marl, kieselguhr or any absorbent material that is not materially changed during combustion of the head. Fillers slow down the speed of burning of the head and thereby allow sufficient time -for the flame transmitter to. operate. These materials (fillers) being inert absorb heat from the burning head.

Wood splints or cardboard strips often iorm the match body. Paraflin wax, stearin or sulphur are used as flame transmitters and are impregnatedinto the splint or cardboard strips.

In this specification, I define a flller as a material preventing too rapid a propagation of flame through the match head. A flame transmitter is a substance that aids in conveying the flame from the match head to the match body.

One object oi my invention is to provide a flller composition containing a nitrated hydrocarbon, or an oxygenated derivative of a nitrated hydrocarbon, that retards too rapid progression oi flame through the head and at the same time produces a hotter flame. Another object is to cause the body oi the match to ignite rapidly by impregnating said body with nitrated hydrocarbons or orwgenated derivatives oi-nitrated hydrocarbons. Other objects will be apparent from the disclosures in this specification.

This invention is applicable to both saiety matches, as well as to the ordinary strike-any where matches.

I have observed that the iollowing groups oi compounds, nitroparafins. nitro mono-and polyhydroxy' alcohols, nitro' substituted aliphatic esters or nitro derivatives .oi 1,l-di(nitro-alkoxy) -alkanes are especially applicable as impregnating agents for fillers or match bodies.

Nitroparaflin wax can be made by reaction oi paraflin wax with nitric acid at a temperature ,aikanes.

slightly above the melting point of the paraflin wax. If desired, a catalyst (e. g., aluminum nitrate) may be used with the acid. Aiter reaction is finished, the wax layer is washed with water to remove the excess nitric acid. Furthermore, the nitrated wax layer can be extracted with acetone, or other appropriate solvent, in which paraifln wax exhibits only a very limited solubility and aiter evaporation of the solvents solid concentrate of nitrated wax can be secured.

Nitrohydroxy compounds, suitable for my purpose, can be made by combining a nitroparaifln with an aliphatic aldehyde. Nitroalcohols or nitroglycol are obtained, depending upon whether one or two moles of aldehyde, respectiveiy, are reacted with one mole of the nitroparaflln. Reaction is carried out in the presence of an inert liquid medium, such as water, alcohol, ethylacetate, and in the presence of an alkaline catalyst, e. g., calcium hydroxide or potassium carbonate. Ii the reaction medium'is water, then the products (after removing any insoluble material by filtration) can be isolated either by extraction with a low-boiling waterimmiscible solvent followed by evaporation of the solvent, or by chilling the aqueous medium'and thereby eiiecting crystallization oi the'i desired material. In case the liquid medium is nonaqueous, after removal of insoluble material it maybe eliminated by distillation and the residue then subjected to an extraction operation or to a recrystallization step, as the case may be.

Esters of the nitroalcohols or oinitroglycols are obtained by interaction oi the nitrohydroxy compound with an acid anhydride. Catalysts, such as hydrogen chloride, are useful in some cases. The product is isolated by pouring the reaction-mixture into a water solution .oi an alkali, whereby the ester separates as a water-insoluble layer and any unreacted acid anhydrid (or acid) is neutralized.

Aldehyles, such as par-aldehyde or paraiormaldehyde, in ether solution combine with nitroalcohols or nitroglycols (invthe presence oi hydrogen chloride, for example) to furnish acetals or iormals, respectively. In most instances, molecular proportions oi the reacting compounds are used. The ether is evaporated from the solution, and the resulting iormal or acetal (obtained as a residue) washed-with water. The acetals and iormals are classed as i,l-di(nitroalkoxy)- I have observed that's. non-combustibleabsorbent material impregnated with one or more of the nitro derivatives oi the group consisting oi nltroparaflins,-nitrohydroxy aliphatics, nitro substituted aliphatic esters or nitrosubstituted l,1-'di(nitroalkoxy) -alkanes forms a lame retarder superior to an unimpregnated filler. The

I nating flllers.

treated flame retarder is equally as efllcient (as the untreated one) in slowing down the flame propagation but at the same time helps produce a hotter flame which ignites the flame transmitter and match body more easily.

impregnation of the flller by the nitro compound or compounds may take place by simple mixing. This method is applicable to solid nitro bodies that can be liquefied (by mild heating) without decomposition and to low or highboiling liquids: Best results are obtained by adding the material to be absorbed slowly to the filler with continuous mixing.

When the impregnating agent is a solid, not readily liquifled, a solution of it may be incorporated with the flller. It is preferable. to use a low-boiling solvent that can be removed readily by mild heating or by spontaneous evaporation at room temperature. The method ofmixns the solution withthe absorbent may be similar to that described previously when a liquid nitro compound Was'the impregnating material.

Other methods commonly used for absorbing one material on another may be employed, in certain instances, where the previously mentioned procedures do not give the desired result,

an example being distillation of an ordinarily solid or liquid compound and absorbing the vapors on a porous body, which would be suitable as a filler. Distillation may be effected at atmospheric or sub-atmospheric pressure as may be necessary with the particular compound employed. vIn some cases it may be desirable to treat the absorbent material with vapors under super-atmospheric pressure.

By proper choice of absorbents, 'the'more volatile nitro compounds can be used and the resulting composition will be stable. Although very little of even the volatile nitrated derivatives are lost by evaporation from the filler, when the match head ignites, the impregnating a ents are readily released and thereby become available to burn and supply extra heat to the burn- 118 head. The extra heat thus produced ignites the flame-transmitter and match body more readily than when an untreated filler is em ployed.

Match head compositions superior to ordinary match head mixtures can be made bysubstitut i 8,,in part or'in whole, an impregnated flller for an untreated one. I

The same compounds may be used for flame transmission as have been described for impreg- The body; of the match may be impregnated by dipp n into a liquid or molten nitro compound or a solution thereof in a volatile solvent. When treating splints or cardboard striDsr-itis important to have a very fluid impregnating bath. The desired consistency may be gained by controlling the temperature or by using mixtures of nitro compounds or mixtures of nitro compounds and ordinary impregnating agents (e. g., paraflin wax or stearin). In some instances, a solvent, in minor proportion, may be employed to control viscosity of the impregnatingmixture. In the last named case, a drying period should be allowed before the head is put on the splint. When the nitro compounds are melted before application, the treated match bodies should be cooled to the point where the impregnating compound becomes solid before the head is applied.

I Solid compounds that decompose on heating or have too high a melting point may be dissolved in an appropriate solvent and this solution used for impregnating the splints. Solvents having a low-boiling point best serve this purpose. A concentrated solution is most desirable and, consequently, solvents that will dissolve a considerable quantity of nitro compound in a small volume of solution are preferred.

Mixtures of nitro compounds or of nitro compounds with ordinary flame transmitters (e. g., parafiln wax or stearin) can be dissolvedin a solvent or in a mixture of solvents and the solution used as in the preceding manner. In any case, where a solvent is employed, it is preferable to evaporate the latter-from thetreated match body before the head is attached.

I have observed that nitroparaflin wax behaves quite differently from paraffin wax on a burning splint or cardboard strip. As the molten wax precedes the flame along the splint, it has a tendency to be absorbed by the match body. Nitroparafiln'wax is not absorbed as rapidly as paraflin wax and, consequently, if the same quantity of both waxes is impregnated into two match splints, the nitro wax will travel farther down the burning splint than the paraffln wax.

The main object of impregnating splints with flame transmitters is to facilitate ignition of the match body. Therefore, the nitroparaflln wax is more eflicient because its flame transmittin power extends farther down the splint. other explanation of this increased efliciency is that less nitro wax is necessary to propagate flame along a given length of stick than when paraffin wax is used. p

Splints treated with .nitroparaflin wax ignite more readily than those treated with paraflin wax. Match bodies which are not impregnated do not become ignited as easily as splints treated with nitro compounds.

The following examples will illustrate more clearly my invention. I do not wish my invention to be limited only to the specific compounds named therein, to the proportions of ingredients mentioned or to methods described.

Example 1.-A nitroalcohol, 2-nitropropanol, was made by the following method. One mole of nitroethane was mixed with an equal volume ofwater. To the water-nitroparaflln mixture 0.5% of calcium hydroxide (based on the weight of nitroparaflin) was added. The whole mixture was stirred vigorously while one mole of formaldehyde in a water solution was added. After wards, the nitroalcohol from the combination of the aldehyde and nitroparaflin was extracted with ethyl ether. The latter was evaporated under reduced pressure and the nitroalcohol, 2-nitropropanol obtainedas'a residue,

Example 2.-Twenty parts of 2-nitropropanoi. as made in Example 1, were admixed with parts of infusorial earth. This alcohol is a liquid Parts KClOa 450 KacrzO'z Treated filler 100 Flowers oi. sulfur 60 Amorphous phosphorus l0 Gum arabic Water Enough to give desired consistency.

The glue was dissolved in a small amount of water, and pulverized potassium chlorate and potassium dichromate were incorporated. After each compound was added, sumcient water was admixed to keep the mixtur in a pasty form that could be easily and safely handled. The filler, flowers of sulfur and phosphorus were incorporated in the order named. The final mixture had the consistency of thick paint. Wood splints were used in making matches with this match head composition. dipped into the head mixture and then dried. These match heads ignited the Splints better than a similar head composition containing an untreated filler.

Example 3.To make the acetal of 2-nitro- 2-propyl-propanediol-13 the following procedure was employed. Two moles of formaldehyde were reacted with one mole of l-nitrobutane in the manner described in Example 1. The resulting nitroglycol was extracted with ethyl ether and the ether evaporated. Two moles of paraldehyde were combined with 3 moles of 2-nitro-2-propylpropanediol-1,3 using dry hydrogen chloride as a catalyst and ethyl ether as the liquid medium. The mixture was allowed to react over The splints were Example 7.-The' formal of 2-nitro-2-methylpropanediol-1,3 was prepared according to the procedure given in Example 3, with the exception that paraformaldehyde was substituted for paraldehyde. r 1

Example 8.Splints were treated with the v formal oI- 2-nitro-2-methylpropanediol-1,3 by

night, and again'dry hydrogen chloride added.

dried. Evaporation of the ether under reduced.

pressure, yielded the acetal as an almost colorless solid. 1

Example 4.Two partsof acetal of 2-nitro-2- propylpropanediol-1,3 were dissolved in four parts of ethyl ether. The solution .of the solid ycol was mixed with four parts infusorial earth. The solvent was allowed to evaporate and the residual product used in the same formula as in Example 2. match head composition were superior to similar matches made with untreated fillers in that after striking they ignited splints more readily. The head flamed smoothly and burned with a hotter flame than when an ordinary filler, e. g., kieselguhr or powdered glass, was used.

Example 5.-Nitrated paraflin wax was prepared in the following manner: Ten parts of the wax were admixed with 12.2 parts of hydrated aluminum nitrate (Al(NOa)3.9H20) as catalyst, and after the mixture was heated to 100 C. then 4.3 parts of nitric acid (sp. gr. 1.42) were added.

The reactants were kept at 100 C. for hours,.

during which time they were vigorously stirred. Also during this period, at approximately 6 hour intervals, there were added 4.3 parts, 4.3 parts and 2.1 parts of nitric acid. The waxy layer was withdrawn, washed well with water to eliminate any entrained acid or catalyst, and then extracted with acetone. After filtering any insoluble material, evaporation of the solvent (acetone) yielded a concentrate of nitrated wax.

Example 6.Nitroparafiln wax, as made in Example 5, was melted and heated to 100 C.- Wood splints were immersed therein to the extent of approximately three-eighths of an inch, withdrawn and the nitrated wax allowed to harden. Heads similar in composition to those described in Example 4 were put on the impregnated splints. These matches were easy to ignite and because the nitro wax is not absorbed into the The matches obtained from this burning splint as'rapidly as ordinary wax, they were superior in burning qualities to matches dride.

dipping into the compound, which is a liquid at ordinary temperature. A short time is'allowed for the formal to be absorbed by the splint and then a head similar in composition to that described in Examule 4 was put onto the match body. The matches, when .dry, ignited easily and much more readily than when untreated splints were used. 4 V

Example 9.-An ester of 2-nitro-2-methylpropanol and acetic acid wr-s made according to the following-directions. "The alcohol was obtained bycondensing formaldehyde with 2-nitropropane as in Example 1. Molecular proportions of the nitroalcoholand acetic anhydride (plus 10% excess) weremixed together. Dry

hydrogen chloride was passed through the solution for a short time and then the reaction was allowed to proceed at room temperature for three or four days. Afterwards, the reaction mixture was poured into a sodium bicarbonate solution to neutralize the excess and unreacted anhy- The acetate separated from the aqueous solution as an insoluble layer and this was withdrawn, washed with. water and dried.

Example 10.The acetate of 2-nitro-2-methylpropanolfrom Example 9 is a liquid. Splints were dipped into the acetate to a depth of threeeighths of an inch, and a few minutes time was allowed for the liquid to be absorbed into the stick. Heads similar in composition to Example 4 were put onto the splints. The matches were dried and when struck, the matches with treated splints became ignited easier than when no treatment was applied to the sticks. 1

Example 11.One part by weight of the acetal of 2-nitro-2-propylpropanediol-1,3, as obtained in Example 3, was dissolved in an equal part of ethyl ether. Splints were dipped into the acetal solution and then gently heated to evaporate the ether. The impregnated splints afterwards were dipped into a match head composition similar to that described in Example 4. The matches, after the head was dried, ignited easily and much better than when the match body was untreated.

It will be seen from the foregoing disclosures that my invention provides matches with improved burning and igniting qualities. It also involves inert and non-combustible flame retarders or fillers which are impregnated with nitro compounds which in turn aid in proldnging or extending the burning period when the match head is ignited by friction. The proportion of filler in the match head composition may vary within rather wide limits, say from about 10 per cent to about 40 per cent. Whatever the proportion employed, it should be suflicient to retard flame progression (on ignition of the match head) and thereby allow the match body (splint, cardboard strip or other combustible material) to become ignited.

Likewise, the proportion of nitro compounds may vary between wide limits. In the examples, I have illustrated filler compositions in which the proportion of nitro bodies was one-half to onefourth that of the inert and non-combustible filler. I do not wish to be limited to these, since greater or lesser proportions may serve equally well in some instances. The quantity of nitro derivative may be as low as 10 per cent of the inert iiller and the resulting composition still function. What is necessary is that a sufficient quantity of the nitro body should be present that it will extend or prolong the initial flame period {after striking the match head) so that the flame transmitter will ignite and in turn kindle the match body. r 1

Those nitro compounds particularly suitable for my invention include not only those aliphatic derivatives obtained by direct nitration or treatment with nitric acid, but also those resulting from the condensation oi nitroparafllns with allphatic aldehydes. The compounds prepared in this manner contain not only a nitro group, but

also a hydroxyl group; Moreover, aliphatic car-v boxylic esters or aliphatic alkoxyderivatives of theseznitrohydroxy compounds are suitable for the purpose.

My invention embraces not only match-head containing flllers'impregnated with the abovementioned nitro compounds, but also match bodies impregnated with such. In this manner,

I secure not only greatly enhanced flame transmission irom the match head to the match body but also superior burning qualities in the match It understood, or course, that not only are individual nitro compoundsor their oxygen-containing derivatives (as mentioned above) included in this invention, but also various mixtures of such V or course, it is possiblelikewise to dip the its lengthwith a nitro compound containing at finger-holding end so that the fingers will not get burned when the match is held for too long a time after ignition.

What I claim is: I g V 1. A- friction-ignitible match; comprising a match head consisting of a friction-ignitible composition attached to a combustible match body impregnated with a nitroparaflln containing at least one nitro group in which the nitrogen atom is directly attached to a carbon atom, the proportion -of"said nitro compound on said body being sumcient' to transmit the flame to said match body from said match head when ignited.

2. A iriction-ignitible match comprising a match head ignitible by friction attached to a match body impregnated for at least a portion of least one nitro group in which the nitrogen atom is directly attached to a carbon atom in a parafllnic hydrocarbon group, said nitro compound being selected from the group consisting of nitroparaihns, nitrohydroxy-parai'flns, aliphatic monocarboxylic esters of nitrohydroxy-paramns, and

nitroalkoxy-paraiilns, the proportionof said nitro positioninwhich is incorporated an inert and non-combustible filler impregnated with a nitro- *paraflln containing at least one nitro group in attached to said match head.

' CARLETON ELLIS; 

